Activation
of 7‑Silanorbornadienes by N‑Heterocyclic
Carbenes: A Selective Way to N‑Heterocyclic-Carbene-Stabilized
Silylenes
Dennis Lutters
Claudia Severin
Marc Schmidtmann
Thomas Müller
10.1021/jacs.6b02824.s005
https://acs.figshare.com/articles/dataset/Activation_of_7_Silanorbornadienes_by_N_Heterocyclic_Carbenes_A_Selective_Way_to_N_Heterocyclic_Carbene_Stabilized_Silylenes/3203983
The synthesis of
hydridosilylenes Ter(H)Si: <b>3a</b> (Ter:
2,6-bis(2,4,6-trimethylphenyl)phenyl) and Ter*(H)Si: <b>3b</b> (Ter*: 2,6-bis(2,4,6-tri<i>iso-</i>propylphenyl)phenyl)
stabilized by the N-heterocyclic carbene (NHC) ImMe<sub>4</sub> is
reported. The synthesis of stabilized hydridosilylenes <b>3</b> was accomplished by a previously unknown NHC-induced fragmentation
of silanorbornadiene derivatives. Structural studies of the stabilized
silylenes <b>3</b> and of its Fe(CO)<sub>4</sub> complex <b>12</b> accompanied by a theoretical analysis of their bonding
situation indicate that stabilized silylenes such as <b>3</b> can be regarded as neutral silyl anion equivalents. A computational
investigation of the reaction course indicate a virtual one-step reaction
between the NHC and the silanorbornadiene. A theoretical assessment
of the scope and limitations of this reaction suggests that it is
general and can be used also for the synthesis of other carbene analogues
such as germylenes and phosphinidenes.
2016-04-27 18:20:05
silylenes 3
Structural studies
NHC
hydridosilylenes 3
ImMe 4
synthesis
reaction course
bi
silanorbornadiene derivatives
silyl anion equivalents
carbene analogues
Selective Way
Ter